Method of separating the constituents of gaseous mixtures



May 26, 1925. 1,539,528

C. C. VAN NUYS IETKOD 0F SEPARATING THE CONSTITUENTS OF GASEOUS IIIXTURES Filed Sept. 9. 1920 Patented May 26, 1925.

UNITED STATES PATENT OFFICE.

CLAUDE C.VAN NUYS, OF NIElW YORK, N. Y., ASSIGNOR'TO AIR REDUCTION COMPANY, INC., A CORPORATION OF NEW YORK.

METHOD OF SEPARATING THE OONSTITUENTS OF GASEOUS MIXTURES.

Application filed September 9, 1920. Serial No. 409,196.

To all whom it may concern:

Be it. known that I, CLAtinn C. VAN NUYs, a citizen of the United States, residing at New York, in the county of New York, State of New York, have invented certain new and useful Improvements in Methods of Sep-. arating the Constituents of Gaseous Mixtures; and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

This invention relates to the liquefaction and separation of the constituents of gaseous mixtures, and is particularly applicable to the recovery of oxygen and nitrogen from the atmosphere, although the principles hereinafter described may be employedin separating the constituents of gaseous mixtures other than air.

Separation of the constituents of a binary gaseous mixture is accomplished in accordance with a well known method by compression and cooling of the mixture, followed by liquefaction in two fractions, at a pressure somewhat below the initial pressure of the mixture. The first liquid frac: tion is obtained by a selective condensation in a tubular condenser employing the principle of backward return so as to obtain a liquidenrichcd in the less volatile constituent to which is added sufficient unenriched liquefied mixture, obtained from a separate condenser called the liquefier, to make up for losses due to heat leakage.

The second fraction. consisting substantially of the more volatile constituent delivcred. at the top of the backward return tubular condenser is, after it has been lique fied by indirect contact with liquids ac cumulated at the bottom of the rectification column, delivered to the rectifier at a' level somewhat higher than the level at which the liquid constituting the first fraction entersthe rectifier. This second liquid fraction is expected to wash the less volatile constituent from the ascending vapors by reciprocal evaporation and condensation, and to thus permit liquefaction of that constituent in -a substantiallypure condition. I

In the normal operation of such a method, an efiluent gas is obtained, which contains amounts of the more easily condensable conbe separated far in excess of'the theoretic minimum, and the escape of this constituent stituent of the original gaseous mixture to I liquid obtained at the bottom of the condenser, is a liquid of maximum possible degree ofenrichment in oxygen, that is, it is that-liquid which will be in phase equilibrium with thegaseous mixture entering'the bottom of the condenser. Under these conditions, it is clear that the amount of unliquefied nitrogen leaving the top of the condenser is a maximum. If the composition in oxygen of the enriched liquid constituting the first fraction is less than the limit composition just specified, then the amount of the second fraction, i. e., the unliquefied nitrogen leaving the top of the tubular condenser will be less. In the normal opera tion of this method, the attempt is generally-made to produce an enriched liquid at the bottom of the tubular condenser whose composition is such, that the amount ofnitrogen leaving the top of the condenser and constituting ultimately the second liquid fraction, is just sufficient to deprive the vapors ascending at the level in the rectification column at which the first liquid fraction is delivered thereto of'the oxygen contained in those vapors.-

p This being the case, it is clear that the' method fails to take advantage of the maxi-- mum possible degree of oxygen enrichment attainable in accordance with the principle of condensation by backward return. On the contrary, this enrichment is carried on only to that point where the amount of unliquefied nitrogen is most suitable for the requirements of the subsequent rectification. Due however, tovunavoidabl variations in quantity and composition o the enriched liquid obtained at the bottqm of the condenser by reason of v'ariationsof operating mixture the consequences of whic carr 1 proved, economical and efiicient manner. 7

conditions, and further by reason of the fact that atmospheric air is not a sim le bina fact wi 1 be noted in the operation of sure proper rectification and obtain substantially pure oxy en, to evaporate and cause to ascend in t e column an excess of oxy en with'the result that upward to 30% of e air treated escapes from the top ofthe rectification column unseparated. This result as stated is, in part, a consequence of the fact that atmospheric air contains, in addition to minute quantities of carbondioxide, moisture and the rare elements, helium, neon, xenon and kr pton, substantially 1% of argon, of whic the saturated vapor pressure corres onding to any temperature is intermediate between those of oxygen and nitrogen at the corresponding temperature. In fact, the boiling oint of argon at ordinary pressures is on y 3 to 4 degrees lower presentl it is found necessary than that of oxygen. Hence, when air is selectivel liquefied with backward return, we shoul ex the argon t ereof contained in the liquid fraction, the argon content of this liquid increasing as the li uefied fraction of the air is increased. If a the argon present in air was contained in the enriched liquid,

then assuming that this argon is not subsequently removed, it would be impossible to obtain oxygen of a purity greater than about 95% since the argon, being 1% of the. whole mixture, would be approximately 5% of the oxygen contained t erein. Actually however, argon will be present both in the enriched liquid delivered at the bottom of the tubular condenser and in the unliquefied residue leaving the top thereof, and the amount of argon leaving the -top will be ater according as the amount of nitrogen rawn therefrom is greater. It is clear, therefore, that it will be of advantage to the oxygen enrichment of the liquid con ensed in and obtained at the bottom of the tubes, to the maximum possible degree.

An object of the' present invention is the provision of a method of rectifying lique-' ed gases to separate the constituents of gaseous mlxtures represented thereby in an im- Further objects of the invention are the provislon of a method operating as hereinafter described and ermitting the recovery of a large portion 0 the energy originally.

employed in raising the gas to ..its initial pressure, and of ap aratus adapted to the accomplishment of t e' objects mentioned.

T he ob'ects and adyantages of the invention will apparent as it is better understood by referenoe to the'following specification and accompanying drawin in which an apparatus which is capable o use'in con- .cally illustrated. The details of varied, and no attempt '8 method, in order to inmg. I

The difliculties heretofore experienced in the separation of gaseous'mixtures by lique ct to find the major portion of nection with the method is di ammatie apparatus may be widel has been made to illustrate such details and thereby obscure the purpose of the drawfaction and rectification as above noted, may be overcome to a large degree by the delivcry to the rectification column of a regulated quantity of a liquid obtained by liquefying only a part of the residual gas drawn from the top of the backward return condenser. This portion of the residual gas is liquefied While still under the condenser pressure by passing it through a coil surrounded by liguids accumulating at the base of the recti cation column and then, after its pressure has been released by a reducing Valve to that of the rectifier, it is employed therein as a clarifying liquid, and thus there is left available a considerable amount of the residual gas 'at the original pressure prevailing in the pressure of the mixture to the point neces sary for operation of the cycle. A considerable portion of the argon content. of 'the original air will be eliminated with the residual gas, rendering it possible to attain a higher purity of oxygen at the base of therectificatlon column with less loss of oxygen in the diluent gas leavihg the top of the column.

In carrying out one embodiment of the method, air for example, compressed and cooled in. the customary manner, is delivered to a column in which 1t is subjected to indirect contact with colder liquid or gaseous .'products, and the portion of the .air thus 1i uefied, is permitted to return in contact with further uantities of air and to accumulate in the ottom of the column. Preferably, though not necessarily, this liquid is I'subjected during its backward. passage to a partial rectification by contact with the incoming air for the purpose of insuring that the li uid will contain the maximum quantity 0 oxygen possible, this being substantially 47% or a composition which is in phase equilibrium with the incoming air. During its u ward passage, the air 1s cooled suflicient y by indirect contact with the cold liquid or gaseous products to separate all of the oxygen and a portion of the nitrogen so that the residual unliquefied gas is substantially nitrogen, a portion which is liqueby the operation lied and utilized as a clarifying liquid in the rectifier while the balance is available for the purposes noted.

The accumulated liquid consisting principally of oxygen and nitrogen, the oxygen being in proportion of approximately 47%, is then delivered to the rectifying compart- -ment through a reducing valve which permits the reduction of pressure and the low temperature necessary in order that liquid oxygen collecting at the bottom of the rectifier may liquefy selectively the incoming air by indirect contact therewith, and be .vaporized thereby. The liquid is delivered to the middle part of the rectification column and descends thence over the'usual trays in contact with vapors risin from the accumulated body of liquid which is vaporized as explained above. A partial rectification is thereby accomplished, and the liquid finally accumulating in the lower liquid compartment is substantially oxygen which is vaporized in cooling additional quantities of the compressed air. The vaporized oxygen may be drawn off at a substantial pressure an after being warmed by heat interchange with the incoming air, it may be expanded in a suitable engine to recover another portion of the work originally expended in raising the air to its initial pressure.

The vapor passing upwardly from the lower part of the rectifier contains a substantial proportion of oxygen and to prevent the escape of the major portion of this oxygen, and thereby increase the efficiency of rectification the proper proportion of liquefied residual gas or nitrogen is delivered to the upper part of the rectifier where it serves as a clarifying liquid, to wash substantially all of the oxygen from the rising vapors. The eflluent vapors leaving the rectifier and consisting substantially of nitrogen, may be expanded after heat interchange with the incoming air to recover energy originally expended in compressing the air.

The argon content of the enriched liquid constituting the first liquid fraction being, of this method less than in the case where the oxygen enrichment of this liquid is carried to a. less degree, the rectification of this liquid may be accomplished without it being necessary to vaporize and pass upward in the column as large an amount of oxygen to prevent the oxygen purity at the base of the column becoming reduced by the presence of argon. Although the argon ing liquid delivered to the'top of the column is greater in this method than in the prior method described, the actual amount of argon in the liquid state delivered to the, top

. of the column will be considerably less in absolute amount since only a portion of the residual gas delivered at the top of thebackward return condenser is liquefied for 'partment 7, a refrigerating chamber or percentage of the clarify- 'ing compartment 11 where it accumulates use as clarifying liquid. Thus the method in addition to possessing the advantage of reducing the actual amount of argon necessary to be eliminated in the rectification column from theoxyg'en product, posseses the further advantage of forcing the actual argon passing through the rectification column to concentrate toward the upper regions of said column and thus to increase Its tendency to elimination with the efiiuentgas.

A further advantage of the method lies in the fact that the ,amount of clarifying liquid'delivered to the top of the column may be regulated independently of the amount of enriched liquid produced in the backward return condenser and thus this regulation may be adapted more closely to the require- 'ments of the enriched liquid and the adjustment may follow more closely any variations in the quantities and composition of the enriched liquid due to variable operating conditions. Another important advantage of the method lies in the fact that it permits the recovery of a large portion of d the energy originally expended in raising the gas to its initial pressure since it renders available a considerable amount of residual gas at the original pressure of the backward return condenser.

With this brief description of the method of operation, the apparatus and mode of ap plying the invention will be more clearly understood with relation to the structure illustrated. It is to be understood, however,

that the method and apparatus are of gen-' eral application and that no limitation is im plied therefore by reference to the atmosphere or to the particular apparatus illustrated. In the drawing, 5 indicates a column having a liquid pot 6, a rectifying e qmiquefier 8, a liquid compartment 9 in which a liquid receptacle 10 is suspended, and upper and lower rectifying chambers 11 and 12. Cold compressed gas is delivered to the pot 6 through a pipe 13 and passes thence through the trays 14, on which liquid accumulates for the purpose of separating any excess of nitrogen from this liquid. The

'7 15, which extend through the gas chamber 8, liquid compartment 9 and receptacle 10 to a head 16. Nitrogen is withdrawn from the head through a pipe 17.

The liquid accumulating in the pot 6 is delivered therefrom through apipe 18 havmg; a reducing valve 19 to the lower rectifyon trays 20 of usual form, and also in a receptacle 21 disposed between the lower trays and provided with a coil 22, one end of which is connected to the pipe 17 while the other communicates with a pipe 23 having a reducing valve 24, which delivers the nitrogen liquefied in the coil to the upper comaseous mixture passes thence through tubes The liquid accumulating in the compartment 9 is substantially pure oxygen and as the liquid is evaporated by indirect contact with the gaseous mlxture in the tubes 15, the

" oxygen is withdrawn through a pipe 26.

' one end of the section B of the exchanger,"

Vapors arising'from the receptacle 10 pass upwardly through the trays and in direct contact, first, with the liquid delivered through the pipe 18, and then with the liquid nitrogen delivered through the pipe 23. In the rectifying compartment, the oxygen in the va or is liquefied and joins the downwardly owing liquid. Nitrogen is at the .same time separated from the downwardly flowing hqui-d and-thus the effluent gas from" I the rectifier becomes substantially pure nitrogen. By proper regulation and control of the amount of liquefied nitrogen delivered to the rectifier, it becomes possible tosepa rate a greater proportion of the oxygen from the incoming air than has heretofore been practicable.

To insure proper transfer of cold from the outgoing gases to the incoming gaseous mixture, an exchanger of temperature is employed comprising a plurality of compart ments A, B, C and D, each compartment .being divided by bafi'les 28, to cause the air 1 to circulate therein about two sets of pipes 29 and 30, through which the gasesescaping from the column are conveyed. The nitrogen, for example, escaping through the pipe 17, is, with the exception of that por-' tion which passes throughthe coil 22, delivered to a compartment 31 at one end of the section D of the exchanger, and passes thence through tubes 29, communicatingwith the compartment to a compartment 32 at the other end of thesection. The nitrogen is delivered by a pipe 33 to'a corresponding compartment 34' of the section C and passes through tubes 29 therein, to a compartment 35. Thence the nitrogen is conveyed through a pipe 36 to a compartment 37 at passes through the tubes 29 of the exchanger to a compartment 38, thence through a pipe 39 to a compartment 40 at the end of the section A of the exchangerwherein it is conveyed through tubes -29,to a compartment 44. From the compartment 41, the nitrogen is withdrawn through a pipe 42 having a'controlling valve 43 and is delivered to the expansion engine 44 where it is expanded with external workand the temperature is accordingly reduced. From the engine, the expanded gas is delivered throu h a pipe 45 to a. compartment 46 at one end of the section B of the exchanger. Thence the gas asses through tubes 30 to a compartment 47 Between the sections A and B. Tubes 30 in section A cbnvey the ex anded gas to a compartment 48 at the end of the section A to which an outlet 50 for the nitrogen is connected.

in any suitable manner.

The oxygen delivered from the column through the pi e26 enters a compartment 51 at the end of t e section D of the exchanger and passes through the tubes 30 in the several sections thereof to a chamber 52 at'the end of the section A whence it is delivered through a pipe 53 having a controlling valve 54 with engine 55 Where the oxygen is expanded' with external work and thereby cooled. From the engine 55 the expanded oxygen is delivered through a pipe 56 to a pro-cooler 57 consisting of a shell 58 and a bundle of tubes 59 about which the incoming 35 air circulates, the air being introduced through a pipe 60 and delivered through a pipe 61. The oxygen from the pipe 56 passes through a bundle of tubes 59 and is delivered I,

through a pipe 62 at substantially atmospheric pressure and temperature and may be stored for suitable use.

The eflluent gas from the rectifier is delivered by the pipe 27 to a compartment 63 of the section D of the exchanger and passes thence through tubes 30 to a compartment 64 whence it travels through tubes 30 in the section C of the exchanger to a compartment 65. From this compartment the gas is withdrawn andis delivered byga pipe 66 to an expanslon engine 67 where the gas is expanded with external work and is consequently cooled. From the engine 67 a pipe 68 conveys the gas t-o'the chamber 8 in the column where the gas circulates about the tubes 15 and servesto cool the incoming air and liquefy portions thereof. From the compartment 8 the gas escapes through a pipe 69 to a compartment 70 at the end of the section D of the exchanger and is de- 9 livered thence through tubes 30 in the sections C and D of theexchanger to a compartment 71. A pipe 72 conveys the gas to a compartment 73 at the end of section B of the exchanger, and the gas is delivered thence through tubes 30in the sections A' and B, to ,a compartment 74. The gas escapes through a pipe 75, controlled by a valve 76 at sub- 'stantially atmospheric pressure and temperature. A portion of the effluent gas may be withdrawn from the pipe 72 through a pipe 76' controlled by a valve 7 7, which delivers the gas to the pre-cooler 57. Thus the precooling of the air may be regulated as desired. The gas thus delivered to the pre- I cooler escapes through .a. pipe 78, and may.-

-be stored for utilization.-

It is to be understood that cooling of chamber 8 may be accomplished by deliver- The nitrogen is delivered at substantially atmospheric temperature and 0 pressure and may be stored for utilization of the expanded effluent gas. In this event, the cold of the expanded effluent gas will be utilized in the exchanger, the change requiring merely a slight rearrangement of the gas conveying pipes. As previously noted, the disposition of the cold expanded gases will depend more or less on the'relative volumes thereof which are available.

The air cooled in the pre-cooler is delivered by a pipe 61 to :1V compressor 79, where it is compressed and delivered through a pipe 80 to a water cooler 81. Thence the compressed and cooled gas is delivered through a pipe 82 to the section A of the exchanger where it travels about the baffles 28, and is delivered through pipes 83, 84:, and 85. to the successive sections of the exchanger where the cooling is completed. The air finally passes from the exchanger through the pipe 13 to the pot 6 at the bottom of the column.

Assuming, therefore, that the apparatus is in operation, it will be seen that the cooled compressed gas is successively subjected to the cooling influence of cold expanded gases and accumulated liquid, and that the liquid fraction resulting, is rectified to produce a liquid as rich in oxygen as is possible under the conditions prevailing. This liquid is subsequently rectified and the vapors produced' are caused to contact with liquid nitrogen in quantity suihcient to insure the separation of substantially all of the oxygen. The products of the method described are substantially pure oxygen, and substantially pure nitrogen, and both gases may be utilized commercially without further treatment. The provision of a regulated supply of liquid nitrogen for rectification purposes not only provides more efficient rectification and separation of the constituents of the gaseous mixture, but it facilitates regulation. and permits balancing the operation in such a way as to insure a maximum output of the product with a minimum of attention. Separation of the constituents of the gaseous m1:-:ture 1S accomplished at a pressure only slightly below the initial pressure to which the gas is raised, and the products escape at the initial pressure, or the pressure of separation. The expansion of the products following liquefaction, and after these products have been warmed by contact with the incoming air, insures the. recovery of a large proportion of the energy consumed in raising the gaseous mixture to its initial pressure. The energy recovered may be employed in compressin further quantities of gas with such additions of energy as are requisite to provide the-necessary pressure.

The apparatus is readily placed in operation since it is self-cooling to a marked degree, and consequently, it is necessary merely to start compression and to direct the prodnets of expansion in the engines to the proper points to quickly decrease the tem-- perature of the apparatus and accumulate a body of liquid therein. Thereafter the operation is substantially automatic as described.

From the foregoing description, it will so I ratus, without departing from the invention,-

or sacrificing any of the advantages thereof.

I claim: a

1. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products thereby producing a liquid containing the constituents and a residual gas, subjecting the liquid to rectification with vapors of, preceding portions thereof, vwithdrawing and dividing the residual gas, liquefying non-selectively a regulated portion thereof and subjecting said vapors to final contact with the liquefied residual gas.

2. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting it to selective'liquefaction by indirect contact with colder products thereby producing anliquid containing the constituents and a residual gas, subjecting the liquid to rectification with vapors of preceding portions thereof, withdrawing and dividing the residual gas, 'liquefying non-selectively a controllable portion thereof, subjecting said vapors to final contact with the liquefied residual gas, and utilizing the remaining portion of the residual gas for the recovery of energy therefrom.

3. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing. and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products thereby producing a liquid contaming the constituents and a residual gas, subject-. ing the liquid to rectification with vapors of preceding portions thereof, withdrawing and dividing the residual gas at the initial pressure, liquefying non-selectively a controllable portion thereof, and subjecting said vapors to fied'residual gas. p

4. A method of separating the constituents of a gaseous mixture by liquefaction -which comprises, compressing and coohng final contact with the liquecover energy;

ucts thereby producing a liquid containing the constituents and aresidual gas, subjecting the liquid to rectification with vapors of precedin portions thereof, 'withdrawing and divi ing the residual gas at the initial pressure, liquefying non-selectively a controllable ortion thereof, subjecting said vapors to al contact with the liquefied residual gas, warming the remaining portion of the residual gas and expanding it to retherefrom.

5. A met od of separating the constituents of a gaseous m1xture by liquefaction which comprises, compressing and'cooling the mixture, subjecting it to selective. liquefaction by indirect contact with colder products, thereby producing a liquid containing the constituents and a residual gas, subjecting the liquid to rectification with vapors of preceding portions thereof, withdrawing and dividin non-selective y a controllable portion thereof by indirect contact with the liquid undergoing rectification and subjecting said vapors to final contact with the liquefied residual gas.

6. A method ofseparating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, sub ecting it to selective liquefaction by indirect contact with colder products, thereby producing a liquid containing the constituents and a residualgas, subjecting the liquid to rectification with vapors of preceding portions thereof, withdrawing and dividin the residual gas, liquefying non-selective y a controllable ortion thereof by indirect contact with t e liquid undergoing rectification, subjecting said va-i pors to final contact with the liquefied residual gas, and utilizing the remaining portion of the residual gas for the recovery of ener therefrom. v

7. method of separating the constituents of a gaseous mixture by liquefaction .I-and rectification which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder roducts, thereby producing a liquid containin the constituents and a residual gas, sub ecting the liquid to rectification with precedin port ons thereof, and dividing the residual as at the initia pressure, liquefying non-se ectively a controllable portion thereof by indinot contact with the liquid undergoing rectification and sub'ecting said vapors to final contact with the iquefied residual gas.

8. A method of separating the constituents of a gaseous mixture by liquefaction and rectification which comprises, compresstive liquefaction by indirect contact the residual gas, liquefyingv tlierefrom.

' residual pzflcandcooling the mixture, subjecting it to with colder'products, thereby producing a liquid containing the constituents and a reand rectification which comprlses, compressi ing and cooling the mixture, subjecting it to selective liquefaction. by indirect contact with colder'products, thereby producing a liquid containing the constituents and a resi ualgas, subjecting the liquid to rectification with precedin portions thereof, withdrawing. and divi ing the residual gas at the initial pressure, liquefying non-selec tively a controllable portion thereof by indirect contact with the 1i uid undergoing rectification, subjectin said vapors to final contact with the lique ed residual gas, subjecting the remaining portion of the residual gas to heat interchange with the incoming mixture and expanding it to recover energy 10. A method of separating the constituents of a gaseous mixture by liquefaction and'rectification which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producing a liquid containing the constituents and a residual gas,' liquefying non-selectively a portion of the residual as, subjecting t e two liquids to recti cation with vapors from preceding portions thereof, and regulatin the supply of liquefied residual gas to re uce the amount of the more readily condensable constituent escaping with them or. p v p 11. method of separating the constituents of a gaseous mixture by liquefaction and rectification which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producin a liquid containing 'the constituents an a gas, .liquefying non-selectively. a portion 0 theresidual gas, subjecting the two liquids to rectification with va ors from preceding ortions thereof, regu ating the supply of uefied residual gas to reduce the amount 0 the more readily condensable constituent escaping with the vapor and utients of a gaseous mixture liquefaction and rectification which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producing a liquid containing the constituents and a residual gas, liquefying non-selectively a portion of the residual gas, subjecting the two liquids to rectification with vapors from preceding portions thereof, regulating the -supply -of liquefied residual gas to reduce which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products thereby producing a liquid containing the constituents and a residual gas, subjecting the liquid to rectification with vapors of preceding portions thereof, withdrawing and dividing the residual gas, liquefying non-selectively a regulated portion thereof, subjecting said vapors to final contact with the liquefied residual gas, collecting one of the constituents as a liquid resulting from' the rectification, evaporating the latter liquid, warming the vapor produced and expanding it to recover energy therefrom.

14. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling. the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producing a'liquid containing the constituents and a residual gas. subjecting the liquid to rectification with vapors of preceding portions thereof, withdrawing the residual gas, liquefying non-selectively a regulated portion thereof by indirect con tactwith the liquid undergoing rectification independently of the liquefaction 'of the original mixture. subjecting said vapors to final contact with the liquefied residual gas, collecting one of the constituents as a liquid resulting from the rectification, evaporating the latter liquid, warming the vapor produced and expanding it to recover energy therefrom. M

15. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producing a liquid and a residual gas, liquefying non-selectively a regulated portion of the residual gas independently of the liquefaction of the original mixture, rectifying the liquid by contact with the incoming mixture and subsequently by contact with vapors arising from preceding portibns of the liquid and finally subjecting the vapors to contact with the liquefied residual gas.

16. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and-cooling the mixture, subjecting it to selective liquefaction by indirect contact with colder products, thereby producing a liquid and a residual gas, withdrawing and dividing the residual gas, liquefyin'g non-selectively a regulated portion thereof, rectifying the liquid first produced by contact first with the incoming mixture and subsequently with vapors arising from preceding portions thereof. finally subjecting the vapors to contact with the liquefied residual gas and-utilizing the remaining portion of the residual gas for therecovery of energy.

17. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting itto a liquefaction operation to separate it into a liquid fraction and a residual gaseous fraction, withdrawing and dividing the gaseou's'fraction,

liquefying non-selectively a regulated portion of the gaseous fraction, rectifying the liquid fraction and employing the liquefied gaseous fraction to reduce the proportion of the more condensable constituent escaping with the vapor from the liquid fraction.

, 18. A method of separating the constitui ents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting 'it to a liquefaction operation to separate it into a liquid fraction and a residual gaseous fraction, withdrawing and dividingthe gaseous fraction, rectifying the liquid fraction and washing the vapor produced by the rectification with liquid produced. by non-selective liquefaction of a regulated portion of the residual gaseous fraction.

19. A method of separating the constituents of a gaseous mixture by liquefaction which comprises, compressing and cooling the mixture, subjecting it to a liquefaction operation to separate it into a liquid fraction and a residual gaseous fraction, withdrawing and dividing the gaseous fraction, rectifying the liquid fraction, washing the vapor produced by the rectification with liquid produced by non-selective liquefaction of a regulated portion of the residual gaseous fraction and utilizing the remaining portion of the residual gaseous fraction for the recovery of energy therefrom.

20. A method ofseparating the constituent's of a gaseous mixture byliquefaction which comprises, compressing and cooling the mixture, subjecting it to a liquefaction operation to separate it into a liquid fraction and a residual gaseous fraction, withdrawing and dividing the gaseous fraction,

rectifying the liquid fraction, washing the vapor produced by the rectification with liquid produced by non-selective liquefaction of a regulated portion of the residual gaseous fraction, utilizing theremaining portion of the residual gaseous fraction for the recover of energy therefrom, eva 0- rating the hqu cl resulting from the rectification and lltlllZlllg the vapor for the recovery of energy therefrom.

/ 21,. A method ofseparating the constitu-' ents of a gaseous mixture by liquefaction, which comprises compressing and cooling the mixture, sub ect1ng 1t to mdirect contact with colder products, thereby pro duo mg a liquid containing the constituents and a residual gas, subjecting the liquid to rectification with vapors of preceding portions.

thereof, withdrawing the residual gas, subjecting a controllable portion thereof to nonselective liquefaction independently of. the treatment of the original gaseous mixture with the liquefied resi ual gas the constitu-' and subjecting said vi ors is aware- 22. A method of separating cuts of gaseous mixtures, w ich comprises compressing and cooling the mixture, subjecting it to indirect contact with colder, products, thereby produc1ng a liquid conand to a liquid consisting chiefly of the most volatile constituent, and contro ling the rectification by liquefying varying portions of-- the residual gas non-selectively and independently of the treatment of the original gaseous mixture to supply the liquid for final rectification of the, vapors.

In testimony whereof I afiix my signa-.

ture.

CLAUDE C. VAN NUYS. 

